US4455442A - Preparation of unsaturated alcohols - Google Patents

Preparation of unsaturated alcohols Download PDF

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Publication number
US4455442A
US4455442A US06/166,857 US16685780A US4455442A US 4455442 A US4455442 A US 4455442A US 16685780 A US16685780 A US 16685780A US 4455442 A US4455442 A US 4455442A
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hydrogenation
catalyst
nme
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Michael Horner
Matthias Irgang
Axel Nissen
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BASF SE
TRW Repa Feinstanzwerk GmbH
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases

Definitions

  • the present invention relates to an improved process for the preparation of olefinically unsaturated alcohols (I) by selective hydrogenation of the corresponding carbonyl compounds (II) in the liquid phase with hydrogen in the presence of a ruthenium, rhodium, osmium, iridium or platinum catalyst.
  • the invention relates to the preparation of unsaturated alcohols of the general formula Ia ##STR1## where R 1 is hydrogen or an organic radical and R 2 , R 3 and R 4 are hydrogen or C 1 -C 4 -alkyl, by selective hydrogenation of ⁇ , ⁇ -unsaturated carbonyl compounds (IIa) ##STR2## the hydrogenation of citral (IIb) ##STR3## to give geraniol and nerol (respectively E- and Z-3,7-dimethylocta-2,6-dien-1-ol; E-Ib and Z-Ib) ##STR4## being of particular importance.
  • J. Am. Chem. Soc. 47 (1925), 3061 et seq. discloses the hydrogenation of cinnamaldehyde by means of platinum catalysts, but the selectivity in respect of cinnamyl alcohol is unsatisfactory. Only if platinum is used together with other catalyst components, such as iron and zinc (Belgian Pat. No. 837,057), iron and silver (U.S. Pat. No. 3,284,517) or cobalt (German Laid-Open Application DOS No. 2,412,517), for the hydrogenation of unsaturated aldehydes, can the formyl group be selectively hydrogenated. Such catalyst systems are however very sensitive and rapidly lose either their activity or their selectivity.
  • this object is achieved by an improved process for the preparation of the unsaturated alcohols (I) by selective hydrogenation of the carbonyl compounds (II) with hydrogen in the presence of a noble metal catalyst, wherein the catalyst used is a ruthenium, rhodium, osmium, iridium or platinum catalyst and the hydrogenation is carried out in the presence of from 5 to 40% by weight, based on (II), of a tertiary amine.
  • a noble metal catalyst wherein the catalyst used is a ruthenium, rhodium, osmium, iridium or platinum catalyst and the hydrogenation is carried out in the presence of from 5 to 40% by weight, based on (II), of a tertiary amine.
  • the process proceeds more successfully and there is a substantial saving in noble metal catalyst, compared to conventional processes. Furthermore, the selectivity in respect of product (I) is improved and is maintained at its original high level for long periods of operation; this is particularly important in the case of fragrances and aromatics, eg. citronellal, since, if an acceptably inexpensive method of purification of the product is used, the yield of the desired product diminishes substantially.
  • tertiary amines examples include aliphatic tertiary amines of a total of 3 to 30 carbon atoms, especially trimethylamine, but also triethylamine, triethanolamine and trihexylamine, cyclic tertiary amines, eg. N-methylpiperidine, N-methylmorpholine and N,N'-dimethylpiperazine, aliphatic-cycloaliphatic tertiary amines, eg.
  • N,N-dimethylcyclohexylamine aliphatic-araliphatic tertiary amines, eg. N,N-dimethylbenzylamine, aliphatic-aromatic tertiary amines, eg. N,N-dimethylaniline and heterocyclic-aromatic tertiary amines, eg. pyridine and quinoline.
  • the amines to be used are very cheap and have a boiling point which is either substantially lower or substantially higher than that of the product, since in these cases either the amine or the product can easily be distilled from the reaction mixture.
  • the amount of amine is preferably from 25 to 40% by weight of the starting material (II).
  • Suitable hydrogenation catalysts are all noble metal catalysts of group VIII of the periodic table, with the exception of palladium, which results in preferred hydrogenation of the olefinic group in the ⁇ , ⁇ -position.
  • the other noble metals, as defined, which can be used may be in the form of an unsupported or, preferably, of a supported catalyst, and it is a particular advantage that according to our observations to date all commercial catalysts containing such metals are of similar suitability. Hence, if the type of catalyst is changed, the operating conditions need only slight modification, if any. Particularly good results in respect of activity and selectivity are achieved with a ruthenium/active charcoal catalyst which has an inner surface area (measured by the BET method) of 600-900 m 2 /g.
  • amount of metal based on amount of starting compound (II), preferably from 0.0001 to 0.1, especially from 0.001 to 0.1, % by weight is used.
  • the reaction is preferably carried out in the presence of a solvent.
  • the amount of solvent is in general from 10 to 300, preferably from 25 to 150, % by weight of (II).
  • Suitable solvents are all inert liquids in which (I), (II) and the tertiary amine are soluble. Examples include the tertiary amines themselves, as well as alcohols, eg. methanol and ethanol, ethers, acetone and hydrocarbons which are liquid under the reaction conditions, eg. hexane and cyclohexane. Methanol is preferred, especially if trimethylamine is used as the tertiary amine, since in this case working up of the reaction mixtures is particularly simple.
  • the hydrogenation is carried out in a conventional manner, ie. at from 20° to 150° C. and under a pressure of from 20 to 200 bar if less than 0.1% by weight, based on (II), of catalyst metal is used, and under a pressure of from 1 to 150 bar if the amount of catalyst is greater than 0.1% by weight.
  • the novel process is of particular importance for the hydrogenation of citral (IIb) to geraniol and nerol (respectively (E-Ib) and (Z-Ib)), since this reaction is known normally to present technical problems due to multiple hydrogenation and isomerization taking place as competing reactions.
  • radicals R 1 in compounds (IIa) may be of any type. If such radicals contain additional olefinic double bonds, these bonds are not attacked.
  • R 1 are alkyl and alkenyl of 1 to 20 carbon atoms and aromatic radicals, eg. phenyl. These radicals may in turn be substituted, for example by alkyl, alkoxy, carbalkoxy, acyl, hydroxyl, carboxyl, nitrile, amino and halogen. Since the principle of the process is unaffected by the nature of the substituents R 1 to R 3 , a detailed recital of the possible starting compounds (IIa) is superfluous.
  • the yields of the products were determined gas-chromatographically and the residue gravimetrically.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US06/166,857 1979-08-24 1980-07-08 Preparation of unsaturated alcohols Expired - Lifetime US4455442A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792934251 DE2934251A1 (de) 1979-08-24 1979-08-24 Verfahren zur herstellung von ungesaettigten alkoholen.
DE2934251 1979-08-24

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US4455442A true US4455442A (en) 1984-06-19

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US (1) US4455442A (enrdf_load_stackoverflow)
EP (1) EP0024648B1 (enrdf_load_stackoverflow)
JP (1) JPS5634641A (enrdf_load_stackoverflow)
DE (2) DE2934251A1 (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5118884A (en) * 1989-10-13 1992-06-02 Institut Francais Du Petrole Hydrogenation of citral
US20040030199A1 (en) * 2002-01-29 2004-02-12 Maughon Robert R. Process for reducing alpha-haloketones to secondary alpha-haloalcohols
CN102295531A (zh) * 2011-09-05 2011-12-28 浙江新和成股份有限公司 一种氢化柠檬醛制备香茅醇的方法
CN103990469A (zh) * 2014-06-05 2014-08-20 金华职业技术学院 用于巴豆醛选择性加氢合成巴豆醇的催化剂及制备方法
CN104368360A (zh) * 2014-11-24 2015-02-25 金华职业技术学院 一种巴豆醛气相选择性加氢合成巴豆醇的催化剂及制备方法
CN109311789A (zh) * 2016-06-07 2019-02-05 巴斯夫欧洲公司 制备2,3-不饱和醇的方法
CN110922298A (zh) * 2019-12-20 2020-03-27 万华化学集团股份有限公司 一种柠檬醛制备香叶醇的方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3130805A1 (de) * 1981-08-04 1983-02-24 Basf Ag, 6700 Ludwigshafen Neue ruthenium/kohle-hydrierkatalysatoren, deren herstellung und verwendung zur selektiven hydrierung von ungesaettigten carbonylverbindungen
DE3722807A1 (de) * 1987-07-10 1989-01-19 Hoechst Ag Neue 3,5-dihydroxycarbonsaeuren und deren derivate, verfahren zu ihrer herstellung, ihre verwendung als arzneimittel, pharmazeutische praeparate und zwischenprodukte
FR2623800B1 (fr) * 1987-12-01 1990-01-26 Rhone Poulenc Sante Procede de preparation d'alcools insatures
FR2623799B1 (fr) * 1987-12-01 1990-01-26 Rhone Poulenc Sante Procede de preparation d'alcools insatures
ES2617222T3 (es) * 2009-04-02 2017-06-15 Basf Se Procedimiento para la preparación de soluciones de compuestos orgánicos, polimerizables por radicales libres, sensibles a la radiación

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284517A (en) * 1963-09-11 1966-11-08 Engelhard Ind Inc Hydrogenation of alpiia, beta-unsaturated aldehydes to alpha, beta-unsaturated alcohols
GB1123837A (en) * 1965-08-13 1968-08-14 Johnson Matthey Co Ltd Catalytic hydrogenation of unsaturated aldehydes
US3655777A (en) * 1968-11-12 1972-04-11 Engelhard Min & Chem Hydrogenation of unsaturated aldehydes to unsaturated alcohols
DE2412517A1 (de) * 1973-03-21 1974-10-03 Hoffmann La Roche Verfahren zur herstellung von alkoholen
BE837057A (fr) * 1974-12-26 1976-04-16 Catalyseur solide pour l'hydrogenation d'aldehydes insatures et procede d'hydrogenation d'aldehydes insatures utilisant ce catalyseur
DE2650046A1 (de) * 1975-11-03 1977-05-05 Rhone Poulenc Ind Verfahren zur herstellung alpha, beta-aethylenisch ungesaettigter alkohole
US4041083A (en) * 1976-09-30 1977-08-09 Rhodia, Inc. Process for the selective hydrogenation of the keto group in nonconjugated olefinic ketones
US4100180A (en) * 1974-12-26 1978-07-11 Teijin, Limited Process for hydrogenating unsaturated aldehydes to unsaturated alcohols

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
FR1489504A (fr) * 1965-08-13 1967-07-21 Johnson Procédé d'hydrogénation des aldéhydes insaturés
DE2357645A1 (de) * 1973-05-29 1974-12-19 Mobil Oil Corp Verfahren zur herstellung von alkohol

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3284517A (en) * 1963-09-11 1966-11-08 Engelhard Ind Inc Hydrogenation of alpiia, beta-unsaturated aldehydes to alpha, beta-unsaturated alcohols
GB1123837A (en) * 1965-08-13 1968-08-14 Johnson Matthey Co Ltd Catalytic hydrogenation of unsaturated aldehydes
US3655777A (en) * 1968-11-12 1972-04-11 Engelhard Min & Chem Hydrogenation of unsaturated aldehydes to unsaturated alcohols
DE2412517A1 (de) * 1973-03-21 1974-10-03 Hoffmann La Roche Verfahren zur herstellung von alkoholen
US3953524A (en) * 1973-03-21 1976-04-27 Hoffmann-La Roche Inc. Catalytic hydrogenation of alpha,beta-unsaturated aldehydes to alpha,beta-unsaturated alcohols
BE837057A (fr) * 1974-12-26 1976-04-16 Catalyseur solide pour l'hydrogenation d'aldehydes insatures et procede d'hydrogenation d'aldehydes insatures utilisant ce catalyseur
US4100180A (en) * 1974-12-26 1978-07-11 Teijin, Limited Process for hydrogenating unsaturated aldehydes to unsaturated alcohols
DE2650046A1 (de) * 1975-11-03 1977-05-05 Rhone Poulenc Ind Verfahren zur herstellung alpha, beta-aethylenisch ungesaettigter alkohole
US4073813A (en) * 1975-11-03 1978-02-14 Rhone-Poulenc Industries Process for the preparation of unsaturated alcohols
US4041083A (en) * 1976-09-30 1977-08-09 Rhodia, Inc. Process for the selective hydrogenation of the keto group in nonconjugated olefinic ketones

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Rylander et al., "Tetrahedron Letters", No. 20, (1969), pp. 1579, 1580.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5118884A (en) * 1989-10-13 1992-06-02 Institut Francais Du Petrole Hydrogenation of citral
US20040030199A1 (en) * 2002-01-29 2004-02-12 Maughon Robert R. Process for reducing alpha-haloketones to secondary alpha-haloalcohols
CN102295531A (zh) * 2011-09-05 2011-12-28 浙江新和成股份有限公司 一种氢化柠檬醛制备香茅醇的方法
CN103990469A (zh) * 2014-06-05 2014-08-20 金华职业技术学院 用于巴豆醛选择性加氢合成巴豆醇的催化剂及制备方法
CN104368360A (zh) * 2014-11-24 2015-02-25 金华职业技术学院 一种巴豆醛气相选择性加氢合成巴豆醇的催化剂及制备方法
CN104368360B (zh) * 2014-11-24 2016-08-24 金华职业技术学院 一种巴豆醛气相选择性加氢合成巴豆醇的催化剂及制备方法
CN109311789A (zh) * 2016-06-07 2019-02-05 巴斯夫欧洲公司 制备2,3-不饱和醇的方法
US11407700B2 (en) 2016-06-07 2022-08-09 Basf Se Process for preparing 2,3-unsaturated alcohols
CN109311789B (zh) * 2016-06-07 2023-04-04 巴斯夫欧洲公司 制备2,3-不饱和醇的方法
CN110922298A (zh) * 2019-12-20 2020-03-27 万华化学集团股份有限公司 一种柠檬醛制备香叶醇的方法

Also Published As

Publication number Publication date
EP0024648B1 (de) 1983-01-26
EP0024648A1 (de) 1981-03-11
DE3061786D1 (en) 1983-03-03
JPS5634641A (en) 1981-04-06
DE2934251A1 (de) 1981-03-26
JPH0113455B2 (enrdf_load_stackoverflow) 1989-03-06

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